Phys 446 Solid State Physics Origin of the energy gaps

Lecture 9 Nov 9, 2007

(Ch. 6.1-6.5)

Last time: Finished with the band theory of metals

Today: Semiconductors

We focused on the energy values

got away from the
zone edges

and
Lecture 9 near the zone edges.

Metals, Insulators, semimetals, semiconductors Tight binding model

Assumptions:
insulator (semi) metal metal – atomic potential is strong, electrons are tightly bound to the ions
– the problem for isolated atoms is solved: know wave functions φn
and energies En of atomic orbitals
– weak overlapping of
atomic orbitals

Start with 1D case

N
1
∑e
ikX j
Bloch function in the form: ψ (k , x) = 1/ 2 φn ( x − X j )
N j =1

where Xj = ja – position of the jth atom, a – lattice constant;

ψn(x- Xj) – atomic orbital centered around the jth atom – large near Xj ,
but decays rapidly away from it.
Small overlap exists only between the neighboring atoms
 ⎛ ka ⎞ The results obtained can be extended to 3D case.
E (k ) = E0 + 4γ sin 2 ⎜ ⎟
⎝ 2 ⎠
For simple cubic lattice, get
Original energy level En has broadened
into an energy band. ⎡ ⎛k a⎞ ⎛ kya ⎞ k a ⎤
E (k ) = E0 + 4γ ⎢sin 2 ⎜ x ⎟ + sin 2 ⎜⎜ ⎟ + sin 2 ⎛⎜ z ⎞⎟⎥
The bottom of the band is E0 ⎝ 2 ⎠ ⎟
⎣⎢ ⎝ 2 ⎠ ⎝ 2 ⎠⎦⎥
- located at k = 0
−1
⎛ d 2E ⎞ Effective mass is
The band width = 4γ – proportional to the overlap integral m* = = 2⎜ ⎟ determined by the
⎜ dk 2 ⎟
⎝ ⎠
For small k, ka/2 << 1 (near the zone center) curvature of
dispersion
E (k ) − E0 = γa 2 k 2 - quadratic dispersion, same as for free electron
=2 1 Generally, anisotropic:
= 2k 2 where m* = - effective mass
E (k ) − E0 =
2m * 2a 2 γ ⎛ 1 ⎞ 1 ∂2E
⎜ ⎟ = 2 i,j = x, y, z - inverse effective mass tensor
For k = π/2, you will find that ⎝ m * ⎠ ij = ∂k i ∂k j
−1
=2 1 ⎛ d 2E ⎞ 1 ∂E 1
m* = − Generally: m* = = 2 ⎜ ⎟ Velocity of the Bloch electron: v = 3D: v= ∇ k E (k )
2a γ
2 ⎜ 2 ⎟
= ∂k =
⎝ dk ⎠

Summary Summary
™ Tight binding model – strong crystal potential, weak overlap. ™Velocity of the Bloch electron: 1
v = ∇ k E (k )
The band width increases and electrons become more mobile =
(smaller effective mass) as the overlap between atomic wave ™In the presence of an electric field the electron
functions increases moves in k-space according to the relation:
™ Concept of effective mass: in a periodic potential electron moves as This is equivalent to the Newton’s second law if we assume that the electron
in free space, but with different mass: momentum is equal to ħk
−1
⎛ 1 ⎞ 1 ∂2E ⎛ d 2E ⎞
2⎜
m* = = ⎟
⎜ ⎟ = 2 i,j = x, y, z ™Dynamical effective mass: ⎜ dk 2 ⎟
⎝ m * ⎠ ij = ∂k i ∂k j ⎝ ⎠
™ Metals: partially filled bands; insulators – at 0 K the valence band is m* is inversely proportional to the curvature of the dispersion.
full, conductance band is empty. In a general case the ⎛ 1 ⎞ 1 ∂2E
⎜ ⎟ = 2 i,j = x, y, z
Semiconductors and semimetals. effective mass is a tensor:
⎝ m * ⎠ ij = ∂k i ∂k j
™ Velocity of the Bloch electron: 1 ™pc = ħk is called the crystal momentum or quasi-momentum.
v= ∇ k E (k )
= The actual momentum is given by ψ k − i=∇ ψ k
remains constant in perfectly periodic lattice 32
1 ⎛ 2m * ⎞ Can show that p = m0v, where m0 is the free electron mass,
™ Density of states. Simple case: D( E ) = ⎜ ⎟ E1 2 v is given by the above expression
2π 2 ⎝ = 2 ⎠
 Physical origin of the effective mass Conductors vs. Semiconductors

Since p = m0v - true momentum, one can write: m dv = F = F + F

0 tot ext L
dt
The total force is the sum of the external and lattice forces.

dv F
But m0 = m0 ext
dt m*
So, we can write
Fext
m* = m0
Fext + FL

The difference between m* and m0 lies in the presence of the lattice force FL

Crystal structure and bonding Carrier density of metals and semiconductors

Semiconductors include a large number of substances of different chemical
and physical properties. Main types of semiconductors:
• Group IV semiconductors - Si, Ge.
- Crystallize in the diamond structure (fcc lattice with a basis composed
of two identical atoms)
- covalent crystals, i.e., the atoms are held together by covalent bonds
- the covalent electrons forming the bonds are hybrid sp3 atomic orbitals
• III-V (GaAs, InP, etc.), II-VI (ZnSe, ZnS) semiconductors and alloys
- zinc blende structure (same as diamond but with two different atoms)
or hexagonal wurtzite structure (GaN)
- also covalent bonds, but polar - the distribution of the electrons Semiconductors have higher
along the bond is not symmetric resistance than metals (~ 10-2 to
• Some other compounds (I-VII, various oxides, halogenides, organic 109 Ohm⋅cm)
semiconductors...) Typical metals: 10-6 Ohm⋅cm
 Temperature dependence of conductivity Band structure
• Semiconductors have the Semiconductor - a solid in which the highest occupied energy band, the
valence band (VB), is completely full at T = 0°K
property that the resistance
increases with decreasing However, the gap above this band is small, so that electrons may be excited
temperature – opposite to metal thermally at room temperature from the valence band to the next-higher band
electron concentration (cm-3)

behavior – the conduction band (VB).

• This is because the number of Electrons are excited across the gap
→ the bottom of the conduction band
conduction electrons changes
is populated by electrons, and the top
dramatically as a function of of the valence band - by holes.
temperature
As a result, both bands are now only
partially full → can carry a current if
an electric field were applied

The energy of the CB has the form:

The energy of the VB may be written as

Temperature (K)
 Band structure parameters of some semiconductors
(room temperature)

The energy gap varies with temperature – due to a change in lattice constant.
This affects the band structure, which is sensitive to the lattice constant.

Band structure parameters of some semiconductors

(room temperature)

The energy gap varies with temperature – due to a change in lattice constant.
This affects the band structure, which is sensitive to the lattice constant.
 Carrier concentration: intrinsic semiconductors
In order to determine the number of carriers, recall the Fermi-Dirac
distribution function:

- probability that an energy level E is occupied by an electron at T

Fermi level in intrinsic

semiconductors lies
close to the middle of
the band gap.

The distribution function and the conduction and valence bands First, calculate the concentration of electrons in the CB.
of a semiconductor:
The number of states in the energy range (E, E + dE) is equal to
De(E)dE, where De(E) - the density of electron states.
Each of these states has an occupation probability f(E) ⇒ the number
of electrons in this energy range is equal to f(E)De(E)dE.
The concentration of electrons throughout the CB is thus given by the
integral over the conduction band:

Eg ~ 1eV >> kT ⇒ can neglect the unity term in the denominator Fe(E)
→

The density of states for the conduction band is given by

The distribution Density of states for
function electrons and holes
substitute expressions for fe(E) and De(E) into the integral, obtain The density of states for the holes is

where Ev is the energy of the valence band edge.

Similarly to the way we did for electrons, can find for the concentration
change the variable and use the result of holes in the valence band:

get

Apply the same ideas to evaluate the number of holes in the VB. For intrinsic semiconductors n = p
The probability that a hole occupies a level E in this band is equal to and
1−fe(E), since fe(E) is the probability of electron occupation
Assuming that the Fermi level lies close to the middle of the band
Solve this for the Fermi energy:
gap, i.e. (µ−E)>>kBT we find for the distribution function of holes:
The second term is very small compared with the first → the Fermi
level is close to the middle of the energy gap.

Substituting µ into the formula for n

gives

where Eg = Ec – Ev
is the band gap.

This also gives the intrinsic hole concentration, since n = p.

n increases very rapidly - exponentially
Ge - with temperature

For Ge at room temperature n ~ 1014 cm-3 -

typical for intrinsic carrier concentration in
semiconductors.
 Impurity states We can calculate the binding energy by using the familiar Bohr model.
Consider, for instance, a sample of Si, which has been doped by As Must take into account the dielectric constant of the medium.
Thus the coulomb potential is now given by
The As atom has five electrons while
Si has valence 4. ε = 11.7 in Si
4 of As electrons form the tetrahedral
bonds with Si. The fifth electron in the Bohr model, the binding energy is
cannot enter the bond, which is now (if me = m0 and ε = 1, get Ry = 13.6 eV)
saturated, and hence this electron
detaches from the impurity. The binding energy of the donor is reduced
Impurities that contribute electrons to the CB of the semiconductors by the factor 1/ε2 (usually ~0.01), and also
are called donors. by the mass factor me/m0 (usually < 1).

Note that electrons have been created without the generation of holes. The binding energy of these shallow donors is
about 10-3 of Ry – agrees with experiment.
 Intermediate Summary
Bohr radius of the donor electron:
™ Semiconductors are mostly covalent crystals with moderate energy
gap (~0.5 – 2.5 eV)
where a0 is the Bohr radius for hydrogen atom, equal to 0.53 Å.
™ Intrinsic carrier concentration
The radius of the orbit >> a0, by a factor of ~100, typically ~50 Å →
much greater than the interatomic spacing.
= p = ni
At room T almost all the donors are ionized → the concentration
of electrons is nearly equal to that of the donors.
™ Fermi level position in intrinsic semiconductor:
Acceptors
Similarly, consider the Si
crystal doped with Ga
atoms. ™ In a doped semiconductor, many impurities form shallow hydrogen-
like levels close to the conductive band (donors) or valence band
(acceptors), which are completely ionized at room T:
n = Nd or p = N a

Statistics of charge carriers in semiconductors. Semiconductor statistics

Electrical conductivity. Mobility. Semiconductors usually contain both donors and acceptors

Electrons in the CB can be created either by

thermal interband excitation or
by thermal ionization of the donors.

Holes in the VB may be generated by

interband excitation, or by thermal excitation
of electrons from the VB into the acceptor level.

In addition, electrons may fall from the donor

levels to the acceptor level.

Finding the concentrations of carriers, both electrons and holes, taking all
these processes into account, is quite complicated.
We shall treat a few special cases, which are often encountered in practice.
 Intrinsic region: Extrinsic region:
Carrier concentration is determined primarily by thermally induced interband For the common doping levels, about 1015 cm-3, the number of carriers
transitions. In this region n = p. supplied by the impurities is large enough to change the intrinsic
concentration appreciably at room temperature.
The intrinsic region: the impurity doping is small.
Two different types of extrinsic regions may be distinguished.
If the concentrations of donors and acceptors are Nd and Na,
the requirement for the validity of the intrinsic condition is: n >>Nd - Na 1) Nd >> Na.
In this case, to a good approximation, n = Nd
n increases rapidly with temperature ⇒ the intrinsic condition becomes more
favorable at higher temperatures. In fact, all semiconductors become intrinsic Hole concentration p is small. To calculate it, note that
at sufficiently high temperatures (unless the doping is unusually high). 32 32
⎛m k T ⎞
n = 2⎜ e B2 ⎟ e
(EF − E g ) k BT ⎛m k T ⎞
p = 2⎜ h B2 ⎟ e − EF k BT
In this case, the carrier concentration is: and
⎝ 2π= ⎠ ⎝ 2π= ⎠

n = p = ni are still valid even for doped sample (here Ev = 0 → Ec = Eg)

3
⎛ k T ⎞ ni 2
np = 4⎜ B 2 ⎟ (me mh )3 2 e g
−E k BT
⇒ = ni 2 ⇒ p=
⎝ 2π= ⎠ Nd
p << Nd = n n-type semiconductor

2) Na >> Nd Electrical conductivity. Mobility

In this case, p = Na n is small Both electrons and holes contribute to electric current.
2
Similarly get ni n << Na = p p-type semiconductor Assume first that a sample is strongly n-type.
n=
Na Conductivity in the free electron model:
Assumed temperature to be high enough so that all impurities are ionized -
True at room temperature. Estimate the value for σe: n = 1014 cm-3 (~10-8 of that in metals); me = 0.l m0

If the temperature is lowered, a point is reached at which the thermal → σe ~ 10-7 (µohm·cm)-1 Typically, in metals σ ~ 1 (µohm·cm)-1
energy becomes too small to cause electron excitation - electrons fall from σ in a semiconductor is still sufficiently large for practical applications
the CB into the donor level →
the conductivity diminishes In semiconductor physics another transport coefficient is often used: mobility
dramatically - freeze-out – µe - proportionality coefficient between the electron drift velocity and the
electrons are now "frozen" applied electric field:
at their impurity sites.
Taking into account that and , we find that
The temperature of freeze-out:
Ed ~ kBT → T ~ 100 K. - mobility is a measure of the rapidity of the electron motion
in the field.
express electrical conductivity in terms of mobility: Dependence of conductivity on temperature

A typical value for µe: σe =10-7 (µohm·cm)-1 and n= 1014 cm-3 Consider a semiconductor in the intrinsic region. In this situation the
concentration n increases exponentially with temperature:
→

Apply the above considerations to the case of holes in a strongly p-type

substance. The conductivity of the holes is given by
We may write the conductivity as Conductivity of Si
versus 1/T in the
where µh is the hole mobility intrinsic range.
where F(T) is a function which depends
General case (both electrons and holes are present): only weakly on the temperature.
When a field is applied, electrons drift opposite to the field and holes drift
in the same direction as the field. When the substance is not in the
intrinsic region, its conductivity is given
The currents of the two carriers are additive ⇒ σ = σe + σh by the general expression
In terms of the mobilities:
where n is the
is in the intrinsic region, n = p, ⇒
intrinsic concentration

Mobility versus temperature: scattering mechanisms These scattering mechanisms are:

In n-type semiconductor: • collisions of electrons with thermally
excited phonons

collision time le varies with temperature ⇒ mobility also varies. • collisions with impurities.
Normally, both le and mobility µe diminish as the temperature rises. At high temperatures, at which collisions
with phonons is the dominant factor, le~ T-1.
Evaluate the conductivity by assuming that ve is the average velocity. In that case, mobility varies as µe ~ T-3/2.
Electrons at the bottom of the conduction band in a semiconductor obey the
classical statistics, not the highly degenerate Fermi statistics, as in metals.
The average velocity can be estimated using the procedure of the kinetic Scattering by ionized impurities dominates
theory of gases: at low temperatures when the phonon
scattering mechanism becomes weak
⇒

le also depends on the temperature - much the same way as it does in metals. Electron mobility versus T
in Ge.
le is determined by the various collision mechanisms acting on the electrons.
 Band structure of real semiconductors Band structure of Si plotted along Ellipsoidal energy surfaces
the [100] and [111] directions corresponding to primary valleys
along the [100] directions.

GaAs,
along the [100] and [111]
directions